Liquid halogenated esters of fatty acids



' NORMAN A. HANSEN AND'DONALEE The amount of halogen controls certainoccurring fats or oils,

have .the important Patented Jan. 5, 1932 UNITED STATES FATE ILLINOIS NTOFFICE L. TAIBERN, OF LAKE BLUFF, ILLINOIS, ASSIGN'ORS TO -ABBOTT-LABORATORIES, OF NORTH CHICAGO, ILLINOIS, A CORPORATION OF LIQUIDHALOGENATED ESTERS OF FATTY ACIDS No Drawing.

It is well known that certain-halogenated vegetable and animal oils maybe prepared by adding the halogen, for example, bromine or iodine, toglycerides of an unsaturated fatty acid, which compose many'animal andVegetable oils and fats. So-called drying oils, preferably semi-dryingoils, are ordinarily employed for this purpose. These halogenated oilsare opaque to X-rays, making possible their use in spaces or cavities ofthe body to permit the sizes and contours of those spaces or cavities tobe visualized.

Many of these halogenated oils, however, are of high viscosity, which isdetrimental for certain therapeutic purposes; furthermore, many of themhave the halogen atoms too loosely bound, so that they decompose toorapidly and produce irritating and deleterious products.

It has now been found that these drawbacks may be avoided by firstpreparing the alkyl esters of the fatty acids which may be obtained bythe saponification of naturally and then halogenating The liquids soobtained advantages of stability, freedom from irritating properties,low toxicity and low viscosity. Additional halogen may be introduced bymaking unsaturated esters, such as allyl esters, of the fatty acids;when halogen is added to these, it combines with the double bonds of theunsaturated alcohol radical, such as the allyl group, as well as withthe unsaturated fatty acid radicals these alkyl esters.

themselves.

It has been found to be preferable to use bromine or iodine as thehalogens, as they are more opaque to X-rays, and these derivatives arereadily produced.

Varying amounts of a halogen, up to saturation, may be introduced intothe alkyl or alkylene esters of the unsaturated fatty acids.

pro erties of the final halogenated esters, such s density, viscosity,opacity to X-rays, etc.

The methods of preparation ly varied. The reactions with halogen may becarried on either with or without a solvent, and with or without acatalyst; the halogen may be added directly, or it may be libermay bewide- Application filed August 13, 1928. Serial No. 299,460.

ated from co pounds of the halogens, introduced into the reactionmixture, such as hydrobromic acid with hypobromous acid, or

hydrobromic acid with some other oxidizing agent; or a hydrogen halide,such as hydrogen bromide or hydrogen iodide, may be added to theunsaturated oil.

The following will illustrate methods by which the halogenated estersmay be PI'G? pared:

Ewamplel One hundred grams of the ethyl esters of the mixed fatty acidsobtained from lard oil is added to fifteen grams of monohydrated sodiumcarbonate. Keeping the temperature at about 20 (3., fifty grams ofbromine is dropped in, with stirring. Filter, using a filtering agent ifdesired. The brominized oil so obtained has a yellowish to amber .color,

and is neutral in reaction. 0

Example 2 The ethyl esters obtained from cottonseed oil may behalogenated in a manner similar to the above, using 60 to 65 grams of.bromine.

Example 3 One hundred grams 'of the ethyl esters ofis then treated witha. decolorizing carbon orkieselguhr, and filtered. The product'soobtained is yellow to amber colored, neutral in reaction, of lowviscisity, and stable.

Example 4 The ethyl esters of the fatty acids obtained from cottonseedoil may be iodized as 2 v nseopsa employed, if it is desired to obtain acompound with a higher iodine content.

Some physical constants of the halogenated esters described above,together with 5 other halogenated esters which have been prepared byanalogous methods, are given herewith:

Mixed acids from Lard Oll 30% bromine 1. l5 Lard oil. 13% bromine 1.0Lard 0ll 40% bromine 1. 27 Lard oil 32% iodine l. 07 Cottonseed oil 38%bromine 1. ard 0' bromine 1.1 15 Cottonseed oil- 35.5% iodine 1.12Castor oil... 30% bromine 1. 22 Soy bean oi 40% bromine 1. 25 Olive oil40% bromine 1.16

The following figures represent the viscosities of certain of theseproducts:

Viscosity of brominized esters (water:1)

Butyl ester, 6.8 (28% Br.) Ethyl ester, 7.5 (38% Br.)

Ethyl ester, 23.6 (43% Br.) Ethyl ester, 12.5 (37% Br.) Ethyl ester,12.1 (40% Br.)

Sesame The scope oftheinvention should be determined by reference to theappended claims, said claims being-construed as broadly as possibleconsistent with the state of the art.

The word oil as found in the claims is used in its generic sense asincluding also fats.

We claim as our invention:

1. A new liquid medicinal substantially opaque to X-rays, comprisinghalogenated ethyl esters of the mixed fatty acids derived fromcottonseed oil.

2. A new liquid medicinal substantially opaque to X-rays, comprisinghalogenated ethyl esters of the mixed fatty acids derived fromcottonseed oil. 7

45 3. A new liquid medicinal comprising a halogenated alkyl ester of anunsaturated fatty acid having a viscosity suffieiently low to enablesaid medicinal to readily enter the smaller cavities of the human body.

4. A new liquid medicinal substantially opaque to X-rays comprising ahalogenated alkyl ester of an unsaturated fatty acid of an oil obtainedfrom the class comprising vegetable and animal oils and fats, saidmedicinal having a viscosity sufficiently low to enable it readily toenter the smaller cavities of the human body.

Aug. 10th, 1928.

NORMAN A. HANSEN. DONALEE L. TABERN.

(Seal) CERTIFICATE OF CORRECTION. Patent No. 1,840,034. I I

'v NORMAN A. HANSEN ET AL.

It is hereby certified that error appears in the v above numbered patentrequiring correction asfollo 1, for "cottonseed" read lard printedspecification of the ws: Page 2, line 40, claim and that the saidLetters Pa'tentshould be read Signed and sealed this 23rd day ofFebruary, -A. D. 1932.

M." J. Moore, .Acting Commissioner of Patents.

Granted January 5; 1932, to

